Origin of Glass-like Thermal Conductivity in Crystalline TlAgTe

Abstract: Ordered crystalline compounds exhibiting ultralow and glass-like thermal conductivity are both fundamentally and technologically important, where phonon quasi-particles dominate their heat transport. Understanding the microscopic mechanisms that govern such unusual transport behavior is necessary to unravel the complex interplay of crystal structure, phonons, and collective excitations of these quasi-particles. Here, we use state-of-the-art first-principles calculations based on quantum density functional theory to investigate the origin of experimentally measured unusually low and glassy thermal conductivity in semiconducting TlAgTe. Utilizing a unifying framework of anharmonic lattice dynamics theory that combine phonon self-energy induced frequency renormalization, particle-like Peierls ($kappa_l^P$) and wave-like coherent ($kappa_l^C$) thermal transport contributions including three and four-phonon scattering channels, we successfully explain the experimental results both in terms of magnitude and temperature dependence. Our analysis reveals that TlAgTe exhibits several localized phonon modes arising from concerted rattling-like vibration of Tl atoms, which show strong temperature dependence and enhanced four-phonon scattering rates that are dominated by Umklapp processes, suppressing $kappa_l^P$ to ultralow values. The ensuing strong anharmonicity induced by local structural distortions, lone-pair electrons, and rattling-like vibrations of the heavy cations lead to a transition from particle-like behavior to wave-like tunneling characteristics of the phonon modes above 40 cm$^-1$, contributing significantly to $kappa_l^C$ which increases with temperature. Our analysis uncovers important structure-property relationship, which may be used in designing of novel materials with tunable thermal conductivity.